Silver halide photographic material and photographic image forming method using the same

Abstract

A silver halide photographic material comprising a support having thereon at least one light-sensitive silver halide emulsion layer, wherein at least one of the silver halide emulsion layer and a hydrophilic colloid layer(s) adjacent thereto contains at least one hydrazine compound represented by the following general formula (I) and at least one compound selected from the group consisting of compounds represented by the following general formula (II) and (III): ##STR1## wherein R 1 represents an aliphatic or aromatic group which has a substituent having a moiety of --O(CH 2 CH 2 O) n --, --O--(CH 2 CH(CH 3 )O) n -- or --O--(CH 2 CH(OH)CH 2 O) n -- (wherein n is an integer of not smaller than 3) as part of a substituent or having a moiety of a quaternary ammonium cation as part of a substituent group, G 1 represents a bivalent bonding group consisting of at least one of --CO--, --COCO--, --CS--, --C(═NG 2 R 2 )--, --SO--, --SO 2 -- or --P(O)(G 2 R 2 )--; G 2 represents a single bond, --O--, --S-- or --N(R 2 )--; R 2 represents an aliphatic group, an aromatic group or a hydrogen atom, and when there are two or more R 2 groups, they may be the same or different; and one of A 1 and A 2 is a hydrogen atom, and the other is a hydrogen atom, an acyl group or an alkyl- or arylsulfonyl group, when R 1 contains said quaternary ammonium cation, the compound further has a counter anion or has an anion group at R 1 to form an inner salt; ##STR2## wherein Y represents a group which is adsorbed to silver halide; X represents a bivalent bonding group comprising an atom or atoms selected from hydrogen, carbon, nitrogen, oxygen and sulfur atoms; A represents a bivalent bonding group; B represents an amino group which may be substituted, an ammonium group or a nitrogen-containing heterocyclic ring; m represents 1, 2 or 3; and n represents 0 or 1; ##STR3## wherein R 1 and R 2 each represents a hydrogen atom or an aliphatic group, or R 1 and R 2 may be combined together to form a ring; R 3 represents a bivalent aliphatic group; X represents a bivalent heterocyclic ring having at least one of hetero-atoms of a nitrogen, oxygen or sulfur atoms; n represents 0 or 1; and M represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, a quaternary ammonium, a quaternary phosphonium or an amidino group; x is 1 when M represents a monovalent atom or group and x is 1/2 when M represents a divalent atom; said compound may be in the form of an addition salt.

What is claimed is: 
     
       1. A silver halide photographic material comprising a support having thereon at least one light-sensitive silver halide emulsion layer, wherein at least one of the silver halide emulsion layer and a hydrophilic colloid layer(s) adjacent thereto contains at least one hydrazine compound represented by the following general formula (I) and at least one compound selected from the group consisting of compounds represented by the following general formula (II) or (III): ##STR20## wherein R 1  represents an aliphatic or aromatic group which has a substituent having a moiety of --O(CH 2  CH 2  O) n  --, --O--(CH 2  CH(CH 3 )O) n  -- or --O--(CH 2  CH(OH)CH 2  O) n  -- (wherein n is an integer of not smaller than 3) as part of a substituent or having a moiety of a quaternary ammonium cation as part of a substituent group, G 1  represents a bivalent bonding group consisting of at least one of --CO--, --COCO--, --CS--, --C(═NG 2  R 2 )--, --SO--, --SO 2  -- or --P(O)(G 2  R 2 )--; G 2  represents a single bond, --O--, --S-- or --N(R 2 )--; R 2  represents an aliphatic group, an aromatic group or a hydrogen atom, and when there are two or more R 2  groups, they may be the same or different; and one of A 1  and A 2  is a hydrogen atom, and the other is a hydrogen atom, an acyl group or an alkyl- or arylsulfonyl group, when R 1  contains said quaternary ammonium cation, the compound further has a counter anion or has an anion group at R 1  to form an inner salt; ##STR21## wherein Y represents a group which is adsorbed to silver halide; X represents a bivalent bonding group comprising an atom or atoms selected from hydrogen, carbon, nitrogen, oxygen and sulfur atoms; A represents a bivalent bonding group; B represents an amino group which may be substituted, an ammonium group or a nitrogen-containing heterocyclic ring; m represents 1, 2 or 3; and n represents 0 or 1; and said compounds represented by formula (II) are represented by formula (II-m), (II-n), or (II-o): ##STR22## wherein M represents an alkali metal atom, an ammonium group or a group which is converted into H or an alkali metal atom under alkaline conditions; --(X) n  --A-B and m are as defined in formula (II); and wherein the heterocyclic rings in the formulas may be substituted by one or more of substituent groups; ##STR23## wherein R 1  and R 2  each represents a hydrogen atom or an aliphatic group, or R 1  and R 2  may be combined together to form a ring; R 3  represents a bivalent aliphatic group; X represents a bivalent heterocyclic ring having at least one of hetero-atom of nitrogen, oxygen and sulfur atoms; n represents 0 or 1; and M represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, a quaternary ammonium, a quaternary phosphonium or an amidino group; x is 1 when M represents a monovalent atom or group and x is 1/2 when M represents a divalent atom; said compound may be in the form of an addition salt. 
     
     
       2. The silver halide photographic material as in claim 1, wherein said substituent for R 1  of general formula (I) is at least one of an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a substituted amino group, a ureido group, a urethane group, an aryloxy group, a sulfamoyl group, a carbamoyl group, an alkylthio group, an arylthio group, a sulfonyl group, a sulfinyl group, a hydroxy group, a halogen atom, a cyano group, --SO 3  M' y , --COOM' y  (wherein M' represents a hydrogen atom, an alkali metal atom, NH 4 , and an alkaline earth metal atom; y is 1 when M' represents a monovalent atom or group, and y is 1/2 when M' represents a divalent atom), an aryloxycarbonyl group, an acyl group, an a alkoxycarbonyl group, an acyloxy group, a carbonamido group, a sulfonamido group, and a phosphoric acid amido group. 
     
     
       3. The silver halide photographic material as in claim 1, wherein R 2  of general formula (I) is substituted with at least one of substituents selected from the group consisting of an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a substituted amino group, a ureido group, a urethane group, an aryloxy group, a sulfamoyl group, a carbamoyl group, an alkylthio group, an arylthio group, a sulfonyl group, a sulfinyl group, a hydroxy group, a halogen atom, a cyano group, --SO 3  M' y , --COOM' y  (wherein M' represents a hydrogen atom, an alkali metal atom, NH 4 , and an alkaline earth metal atom; y is 1 when M' represents a monovalent atom or group and y is 1/2 when M' represents a divalent atom), an aryloxycarbonyl group, an acyl group, an alkoxycarbonyl group, an acyloxy group, a carbonamido group, a sulfonamido group, a phosphoric acid amido group, and a nitrogen containing aromatic ring which may be fused with a benzene ring or a heterocyclic ring. 
     
     
       4. The silver halide photographic material as in claim 1, wherein R 1  of general formula (I) and R 2  of general formula (I) each has at least one of a ballast group and an adsorption enhancing group to silver halide grains. 
     
     
       5. The silver halide photographic material as in claim 1, wherein R 1  of general formula (I) is a group represented by the following general formula (Ia), (Ib), (Ic) or (Id): ##STR24## wherein L 1  and L 2  each represents --CONR 7  --, --NR 7  CONR 8  --, --SO 2  --NR 7  -- or --NR 7  SO 2  NR 8  --; R 7  and R 8  each represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms; and l and m each represents 0 or 1; R 3  and R 4  each represents a bivalent aliphatic group, aromatic group, a combination thereof, or a bivalent group composed of a combination of an aliphatic group and/or an aromatic group with at least one of --O--, --CO--, --S--, --SO 2  and --NR 9  -- [R 9  has the same meaning as R 7  in general formulas (Ia), (Ib) and (Ic)]; R 5  represents an aliphatic group, an aromatic group or a combination thereof; Z 1  represents an atomic group required for forming a nitrogen-containing aromatic ring which may be fused with a benzene ring or with a heterocyclic ring; when l=1 X.sup.⊖  represents a counter anion or a counter anion moiety and when l=0 Z 1  or R 6  has an anion to form an inner salt; R 6  represents an aliphatic or aromatic group; R 6  group in formula (Ic) may be combined together to form a ring; Z 1  and R 6  may be substituted; L 3  represents --CH 2  CH 2  O-- group, --CH 2  CH(CH 3 )O-- group or --CH 2  CH(OH)CH 2  O-- group; and n is an integer of not smaller than 3. 
     
     
       6. The silver halide photographic material as in claim 1, wherein the heterocyclic ring in formula (II-m) to (II-o) is substituted with at least one of a nitro group, a halogen atom, a mercapto group, a cyano group, an alkyl group, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyl- and aryl-sulfonyl group, a carbamoyl group, a sulfamoyl group, an alkyl- and aryl-carbonamido group, an alkyl- and aryl-sulfonamido group, an acyloxy group, an alkyl- and aryl-sulfonyloxy group, a ureido group, a thioureido group, an acyl group, a heterocyclic group, an alkyl- and aryl-oxycarbonyl group, an alkyl- and aryloxycarbonylamino group, an amino group, --COOM', --SO 3  M' (wherein M' represents a hydrogen atom, an alkali metal atom or NH 4 ), and a hydroxy group; said substituents may be further substituted with at least one of these substituents. 
     
     
       7. The silver halide photographic material as in claim 1, wherein the bivalent bonding group represented by X is --S--, --O--, --N(R 1 )--, --C(O)O--, --OC(O)--, --C(O)N(R 2 )--, --N(R 3 )C(O)--, --SO 2  N(R 4 )--, --N(R 5 )SO 2  --, --N(R 6 )C(O)N(R 7 )--, --N(R 8 )C(S)N(R 9 )--, --N(R 10 )C(O)O--, --SO 2  --, --C(O)--, --(O)S(O)O--, or --O(O)S(O)--, said bonding group may be bonded to Q through a straight-chain or branched alkylene group, wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9  and R 10  each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group or unsubstituted aralkyl group. 
     
     
       8. The silver halide photographic material as in claim 1, wherein A represents a bivalent bonding group selected from a straight-chain or branched alkylene group, a straight-chain or branched alkenylene group, a straight-chain or branched aralkylene group an arylene group, and a combination of at least one of these groups with at least one of bivalent bonding group represented by X in formula (I). 
     
     
       9. The silver halide photographic material as in claim 1, wherein said substituted or unsubstituted amino group represented by B is a group represented by formula (II-b): ##STR25## wherein R 11  and R 12  each represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group or a substituted or unsubstituted aralkyl group, and R 11  and R 12  may be combined together to form a saturated or unsaturated hetero ring, or may be cyclized so as to form a saturated hetero ring further having, as a member of the ring, at least one heteroatom. 
     
     
       10. The silver halide photographic material as in claim 9, wherein the substituent group for each of R 11  and R 12  is selected from --COOM', --SO 3  M' (wherein M' represents a hydrogen atom, an alkali metal atom or NH 4 ), a cyano group, a halogen atom, a hydroxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group having not more than 20 carbon atoms, an alkoxy group having not more than 20 carbon atoms, a monocyclic aryloxy group having not more than 20 carbon atoms, an acyloxy group having not more than 20 carbon atoms, an acyl group having not more than 20 carbon atoms, a carbamoyl group, a sulfamoyl group, an acylamino group having not more than 20 carbon atoms, a sulfonamido group, a carbonamido group having not more than 20 carbon atoms, a ureido group having not more than 20 carbon atoms and an amino group, said substituents may be further substituted with at least one of these substituents. 
     
     
       11. The silver halide photographic material as in claim 1, wherein said ammonium group represented by B is a group represented by formula (II-c): ##STR26## wherein R 13 , R 14  and R 15  each represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group or a substituted or unsubstituted aralkyl group; Z.sup.⊖  represents an anion; and p represents 0 or 1 and when the compound forms an inner salt, p is 0 and at least one of R 13 , R 14  and R 15  has an anion. 
     
     
       12. The silver halide photographic material as in claim 1, wherein the aliphatic group represented by R 1  or R 2  in formula (III) is an aliphatic group substituted with at least one of a substituted or unsubstituted phenyl group, an alkoxy group, an alkylthio group, a hydroxy group, --COOM', --SO 3  M' (wherein M' represents a hydrogen atom, an alkali metal atom or NH 4 ), an alkylamino group and an amido group. 
     
     
       13. The silver halide photographic material as in claim 1, wherein the bivalent aliphatic group represented by R 3  in formula (III) is --R 4  -- or --R 4  S-- wherein R 4  is a bivalent aliphatic group. 
     
     
       14. The silver halide photographic material as in claim 1, wherein said compound represented by formula (I) is incorporated in an amount of 1×10 -6  to 5×10 -2  mol per mol of silver halide into the emulsion layer or the adjacent hydrophilic colloid layer(s) to the emulsion layer. 
     
     
       15. The silver halide photographic material as in claim 1, wherein the total amount of the compounds represented by formulas (II-m) to (II-o) and (III) is 1×10 -3  to 0.5 g per m 2  of the photographic material. 
     
     
       16. A method for forming a photographic image by processing a silver halide photographic material with a developing solution having a pH of 9.6 to 11.0, said silver halide photographic material comprising a support having thereon at least one light-sensitive silver halide emulsion layer, wherein at least one of the silver halide emulsion layer and a hydrophilic colloid layer(s) adjacent thereto contains at least one hydrazine compound represented by the following general formula (I) and at least one compound selected from the group consisting of compounds represented by the following general formula (II) or (III): ##STR27## wherein R 1  represents an aliphatic or aromatic group which has a substituent having a moiety of --O(CH 2  CH 2  O) n  --, --O--)CH 2  CH(CH 3 )O) n  -- or --O--(CH 2  CH(OH)CH 2  O) n  -- (wherein n is an integer of not smaller than 3) as part of a substituent or having a moiety of a quaternary ammonium cation as part of a substituent group, G 1  represents a bivalent bonding group consisting of at least one of --CO--, --COCO--, --CS--, --C(═NG 2  R 2 )--, --SO--, --SO 2  -- or --P(O) (G 2  R 2 )--; G 2  represents a single bond, --O--, --S-- or --N(R 2 )--; R 2  represents an aliphatic group, an aromatic group or a hydrogen atom, and when there are two or more R 2  groups, they may be the same or different; and one of A 1  and A 2  is a hydrogen atom, and the other is a hydrogen atom, an acyl group or an alkyl- or arylsulfonyl group, when R 1  contains said quaternary ammonium cation, the compound further has a counter anion or has an anion group at R 1  to form an inner salt; ##STR28## wherein Y represents a group which is adsorbed to silver halide; X represents a bivalent bonding group comprising an atom or atoms selected from hydrogen, carbon, nitrogen, oxygen and sulfur atoms; A represents a bivalent bonding group; B represents an amino group which may be substituted or unsubstituted, an ammonium group or a nitrogen-containing heterocyclic ring; m represents 1, 2 or 3; and n represents 0 or 1; and said compounds represented by formula (II) are represented by formula (II-m), (II-n), or (II-o): ##STR29## wherein M represents an alkali metal atom, an ammonium group or a group which is converted into H or an alkali metal atom under alkaline conditions; --(X) n  --A--B and m are as defined in formula (II); and wherein the heterocyclic rings in the formulas may be substituted by one or more of substituent groups; ##STR30## wherein R 1  and R 2  each represents a hydrogen atom or an aliphatic group, or R 1  and R 2  may be combined together to form a ring; R 3  represents a bivalent aliphatic group; X represents a bivalent heterocyclic ring having at least one of hetero-atom of nitrogen, oxygen and sulfur atoms; n represents 0 or 1; and M represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, a quaternary ammonium, a quaternary phosphonium or an amidino group; x is 1 when M represents a monovalent atom or group and x is 1/2 when M represents a divalent atom; said compound may be in the form of an addition salt. 
     
     
       17. The method as claimed in claim 16, wherein the developing solution is free of an amino compound having a nucleation accelerating characteristic.